JP2017137415A - Chiral rare earth complex polymer and optical functional material using the same - Google Patents

Abstract

（Ａは２価の有機基；Ｌはアセチルアセトン基；ＡとＬの少なくともいずれか一方は光学活性；Ｒ^１〜Ｒ^４は夫々独立に置換／非置換の１価の芳香族基；ｎは１〜２０の整数；ｍは１〜４の整数；ｌは１〜１０００００の整数；Ｌｎは３価の希土類イオン）
【選択図】なしThe present invention provides a rare earth complex polymer exhibiting chiral optical properties and an optical functional material using the same.
A rare earth complex polymer represented by formula (1). A rare earth complex polymer which is preferably an optical acetylacetone group having perfluoroalkyl or alkyl.

(A is a divalent organic group; L is an acetylacetone group; at least one of A and L is optically active; R ^{1 to} R ⁴ are each independently a substituted / unsubstituted monovalent aromatic group; M is an integer of 1 to 4; l is an integer of 1 to 100,000; Ln is a trivalent rare earth ion)
[Selection figure] None

Description

  The present invention relates to a chiral rare earth complex polymer exhibiting chiral optical properties and an optical functional material using the same.

  Circularly polarized light emission (CPL) and circular dichroism (CD) are chiral optical properties. Circularly polarized light is light that draws a circle as the electric and magnetic field vibrations propagate, and includes right-handed circularly polarized light and left-handed circularly polarized light.

  In recent years, optical functional materials exhibiting circularly polarized light emission have attracted attention as raw materials for three-dimensional display displays and security inks. Currently, a technology that combines a circularly polarized light filter with a liquid crystal that emits linearly polarized light is used in a three-dimensional display. The improvement of energy efficiency can be expected. In addition, security ink can provide right circularly polarized light and left circularly polarized light as security information, and development of ink having high security can be expected. One such optical functional material is a rare earth complex. For example, Patent Documents 1 and 2 report rare earth complexes in which a phosphine oxide ligand and an acetylacetone derivative ligand are coordinated to a rare earth ion. It has been found that these rare earth complexes selectively emit right-handed circularly polarized light and left-handed circularly polarized light, that is, have a circularly polarized light emission property, by an asymmetric ligand field derived from the structure.

  On the other hand, optical functional materials such as those mentioned above are often mixed with plastic materials, but generally they need to be melted and molded at high temperatures (about 300 ° C for polycarbonate products), and the light emitters have sufficient heat durability. Is required. As such a light-emitting body having heat resistance, for example, a rare earth complex polymer described in Patent Document 3 has been reported.

JP 2003-327590 A WO2008 / 111293 WO2012 / 150712

  As a rare earth complex polymer having high heat durability, Patent Document 3 discloses tris (hexafluoroacetylacetonate) {4 having a structure in which an Eu complex having an acetylacetone derivative ligand is cross-linked with a morphine oxide bidentate ligand. Although 4′-bis (diphenylphosphoryl) biphenyl} europium polymer has been reported, these rare earth complex polymers do not have chiral optical properties such as circularly polarized light emission and circular dichroism.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the rare earth complex polymer represented by the general formula (1) has high thermal stability and chiral optical physical properties. It came to be completed.

That is, the present invention
General formula (1)

(In the formula, A represents a divalent organic group, L represents an acetylacetone group, and at least one of A and L is optically active. R ¹ , R ² , R ³ and R ⁴ are each independently Represents an alkyl group having 1 to 10 carbon atoms, or a monovalent aromatic group which may have a substituent, n represents an integer of 1 to 20, and m represents an integer of 1 to 4. Represents an integer of 1 to 100000. Ln represents a trivalent rare earth ion.
The present invention also provides a general formula (5)

Represented ^(wherein, R ^{1, R 2, R 3, R 4} , A and n are ^R 1 in the general formula (1) ^{represents R 2, R 3, R 4} , A and n synonymous.) In Phosphine oxide;
General formula (6)

(Wherein Y represents a coordination molecule. J represents an integer of 0 to 6. L, Ln and m have the same meaning as L, Ln and m in formula (1)). The present invention relates to a method for producing a rare earth complex polymer.

  The present invention relates to an optical functional material including a rare earth complex polymer represented by the general formula (1).

  The present invention also relates to a circularly polarizing filter comprising a rare earth complex polymer represented by the general formula (1).

  Furthermore, the present invention relates to an ink comprising a rare earth complex polymer represented by the general formula (1).

  Hereinafter, the present invention will be described in more detail.

  A in the general formula (1) represents a divalent organic group, and the divalent organic group includes an arylene group, a furan-diyl group, a thiophene-diyl group, and a phenylcarbazole-diyl group represented by the general formula (3). Such as heteroarylene groups, methylene groups, and the like, which may have a substituent, and may be linear or branched. Among these, an arylene group represented by the general formula (3) is particularly preferable.

(In the formula, n represents the same meaning as n in formula (1). R ¹² represents a halogen atom or an alkyl group having 1 to 6 carbon atoms, and k represents a substitution in a ring to which R ¹² is bonded to 0 to R ^12. It is an integer up to the number of possible sites.When k is 2 or more, the plurality of R ¹² may be the same or different.
The arylene group represented by the general formula (3) preferably used in the general formula (A) includes a phenylene group, a biphenylene group, a terphenylene group, a quaterphenylene group, a kink phenylene group, a sexiphenylene group, and a naphthalene. -Diyl group, anthracene-diyl group, binaphthyl-diyl group, phenanthrene-diyl group, fluorene-diyl group, etc. are mentioned, and among them, phenylene group and biphenylene group are preferable.

  Ln in the general formula (1) represents a trivalent rare earth ion, and specific trivalent rare earth ions include Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and the like. Among them, Eu is preferable.

  L in the general formula (1) represents an acetylacetone group, an optically active acetylacetone ligand of the general formula (2) is preferable, and an acetylacetone ligand of the general formula (2a) is particularly preferable.

  In the rare earth complex polymer of the present invention, at least one of A and L is optically active. By satisfying the above requirements, the rare earth complex polymer of the present invention has chiral optical properties and becomes an excellent optical functional material.

First, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R in the general formulas (1), (2), (2a), (3), (4) ⁹ , definitions of R ¹⁰ , R ¹¹ and R ¹² will be described.

The alkyl group having 1 to 10 carbon atoms of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) may be linear, branched or cyclic, specifically a methyl group or an ethyl group Propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl Group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethyl Butyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl 3,3-dimethylbutyl group, cyclohexyl group, cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, adamantyl group and the like, which may have a substituent 1 The valent aromatic group includes a phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, p-trifluoromethylphenyl group, m-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 2 , 4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethylphenyl group, 3,5-diethylphenyl Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dip Pyrphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4 -Butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butylphenyl group, 4-tert-butylphenyl group, 2,4-di Examples thereof include a -tert-butylphenyl group and a 3,5-di-tert-butylphenyl group. A phenyl group is preferred in that the rare earth complex polymer (1) of the present invention has optical properties suitable as an optical functional material.

The alkyl group having 1 to 6 carbon atoms of R ^{5 in} the general formula (2) may be linear, branched or cyclic, and specifically, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl Group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group , Cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl Group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group Cyclohexyl group, cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, etc., and the C1-C6 perfluoroalkyl group includes trifluoromethyl group, pentafluoroethyl group , Heptafluoropropyl group, isoheptafluoropropyl group, nonafluorobutyl group, isononafluorobutyl group, sec-nonafluorobutyl group, tert-nonafluorobutyl group, undecafluoropentyl group, nonafluorocyclopentyl group, trideca Examples thereof include a fluorohexyl group and an undecafluorocyclohexyl group. A methyl group, a tert-butyl group, a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group is preferable in that the rare earth complex polymer (1) of the present invention has optical properties suitable as an optical functional material. A fluoromethyl group or a heptafluoropropyl group is particularly preferred.

Examples of the halogen atom of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in} the general formulas (2a) and (4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic. Specifically, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl Group, sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutyl Methyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1, 1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, cyclopentyl Examples thereof include a methyl group, a 1-cyclobutylethyl group, a 2-cyclobutylethyl group and the like. Examples of the methylene sulfonic acid derivative group include a methylene sulfonic acid group, a methylene sulfonic acid methyl group, a methylene sulfonic acid ethyl group, and a methylene sulfone. Examples include an acid propyl group and an isopropyl group of methylene sulfonate. In view of being inexpensive, hydrogen or a methyl group is preferable.

Examples of the halogen atom represented by R ^{12 in} the general formula (3) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 6 carbon atoms is linear, branched, and Any of cyclic | annular form may be sufficient and, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, 1- Ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, cyclobutylmethyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3- Methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-di- Examples include methylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, cyclohexyl group, cyclopentylmethyl group, 1-cyclobutylethyl group, 2-cyclobutylethyl group, etc. can do. A methyl group is preferred because it is inexpensive.

X ¹ and X ^{2 in} the general formula (2) are bonded to each other to form a ring structure, and the ring structure may have a substituent or a double bond. Any structural isomer derived from the double bond position may be used. Specific ring structures include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopropene, cyclobutene, cyclobutadiene, cyclopentaene, cyclopentadiene, cyclohexaene, cyclohexadiene, benzene, cycloheptaene, Cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, pyrrolidine, piperazine, pyrrole, imidazole, pyridine, tetrahydrofuran, furan, tetrahydrothiophene, thiophene, bicyclo [2.1.0 ] Pentane, bicyclo [3.1.0] hexane, bicyclo [2.2.0] hexane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] Butane, 1,7,7-trimethylbicyclo [2.2.1] heptane, bicyclo [2.2.1] heptaene, bicyclo [2.2.1] heptadiene, bicyclo [2.2.2] octane, bicyclo [3.2.1] octane, adamantane and the like can be mentioned, and 1,7,7-trimethylbicyclo [2.2.1] heptane is preferable.

  N of general formula (1) and (3) represents the integer of 1-20, Preferably it is 1-3.

  M in the general formula (1) represents an integer of 1 to 4, and is preferably 3.

  L of General formula (1) represents the integer of 1-100,000, Preferably it is 3-10000.

  In general formula (3), k represents an integer of 0 to 4, and is preferably 0.

  Specific examples of the rare earth complex polymer (1) of the present invention include tris {(+)-3- (trifluoroacetyl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium polymer, tris {(−). -3- (trifluoroacetyl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium polymer, tris {(+)-3- (heptafluorobutyryl) camphor} {1,4-bis (diphenylphosphoryl) ) Benzene} europium polymer, tris {(−)-3- (heptafluorobutyryl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium polymer, tris {(+)-3- (acetyl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium poly -, Tris {(-)-3- (acetyl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium polymer, tris {(+)-3- (pivaloyl) camphor} {1,4-bis ( Diphenylphosphoryl) benzene} europium polymer, tris {(−)-3- (pivaloyl) camphor} {1,4-bis (diphenylphosphoryl) benzene} europium polymer, tris {(+)-3- (trifluoroacetyl) camphor } {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris {(−)-3- (trifluoroacetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris { (+)-3- (Heptafluorobutyryl) camphor } {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris {(−)-3- (heptafluorobutyryl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris {(+)-3- (acetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris {(−)-3- (acetyl) camphor} {4,4′-bis (diphenyl) Phosphoryl) biphenyl} europium polymer, tris {(+)-3- (pivaloyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer, tris {(−)-3- (pivaloyl) camphor} { 4,4′-bis (diphenylphosphoryl) biphenyl} U An example is a ropium polymer. A complex polymer of the general formula (4) is preferable in that it has suitable optical properties, and in particular, tris {(+)-3- (trifluoroacetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium. The polymer, tris {(−)-3- (trifluoroacetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer is preferred.

  Next, the manufacturing method of the rare earth complex polymer (1) of this invention is demonstrated. This production method is a method for producing a rare earth complex polymer (1) by reacting a phosphine oxide (5) and a rare earth complex (6).

(In the formula, A represents a divalent organic group, L represents an acetylacetone group, and at least one of A and L is optically active. R ¹ , R ² , R ³ and R ⁴ are each independently , An alkyl group having 1 to 10 carbon atoms, or a monovalent aromatic group which may have a substituent, Y represents a coordination molecule, n represents an integer of 1 to 20, and m represents 1. Represents an integer of ˜4, j represents an integer of 0 to 6, l represents an integer of 1 to 100,000, and Ln represents a trivalent rare earth ion.)
Specific examples of the phosphine oxide represented by the general formula (5) include 1,4-bis (diphenylphosphoryl) benzene, 4,4′-bis (diphenylphosphoryl) biphenyl (dpbp), 4,4 ″- Bis (diphenylphosphoryl) terphenyl, 4,4 ′ ″-bis (diphenylphosphoryl) quaterphenyl, 4,4 ″ ″-bis (diphenylphosphoryl) kinkphenyl, 4,4 ′ ″ ″-bis (Diphenylphosphoryl) sexiphenyl, 1,4-bis (diphenylphosphoryl) naphthyl, 9,10-bis (diphenylphosphoryl) anthracene, 4,4′-bis (diphenylphosphoryl) -1,1′-binaphthyl, 2,7- Bis (diphenylphosphoryl) phenanthrene, 2,7-bis (diphenylphosphoryl) -9,9-dimethyl-9H-fluoro 2,5-bis (diphenylphosphoryl) thiophene, 2,5-bis (diphenylphosphoryl) furan, 5,5′-bis (diphenylphosphoryl) bithiophene, 5,5′-bis (diphenylphosphoryl) bifuran, 3, 6-bis (diphenylphosphoryl) -9-phenylcarbazole, 1,1-bis (diphenylphosphoryl) methane, 1,2-bis (diphenylphosphoryl) ethane, 1,3-bis (diphenylphosphoryl) propane, 1,4- Bis (diphenylphosphoryl) butane, 1,5-bis (diphenylphosphoryl) pentane, 1,6-bis (diphenylphosphoryl) hexane, 1,4-bis (ditolylphosphoryl) benzene, 4,4′-bis (ditolyl) Phosphoryl) biphenyl, 1,4-bis (dimethylphosphoryl) benzene, 4, 4′-bis (dimethylphosphoryl) biphenyl, 1,4-bis (diethylphosphoryl) benzene, 4,4′-bis (diethylphosphoryl) biphenyl, 1,4-bis (diisopropylphosphoryl) benzene, 4,4′-bis (Diisopropylphosphoryl) biphenyl, 1,4-bis (ditert-butylphosphoryl) benzene, 4,4′-bis (ditert-butylphosphoryl) biphenyl, 1,4-bis (dicyclopentylphosphoryl) benzene, 4,4 '-Bis (dicyclopentylphosphoryl) biphenyl, 1,4-bis (dicyclohexylphosphoryl) benzene, 4,4'-bis (dicyclohexylphosphoryl) biphenyl, 1,4-bis (diadamantylphosphoryl) benzene, 4,4'- Bis (didiadamantylphosphoryl) biphenyl, etc. Can be illustrated. 1,4-bis (diphenylphosphoryl) benzene or 4,4′-bis (diphenylphosphoryl) biphenyl is preferred in that the rare earth complex polymer (1) of the present invention has optical properties suitable as an optical functional material.

  Y in the general formula (6) represents a coordination molecule and is not limited as long as it does not inhibit the reaction. Specific examples include water, heavy water, tetrahydrofuran, pyridine, imidazole, acetone, methanol, ethanol, propanol, and isopropanol. Preferably, it is water.

  J in the general formula (6) represents an integer of 0 to 6, preferably 2.

  Specific examples of the rare earth complex (6) include tris {(+)-3- (trifluoroacetyl) camphor} europium hydrate, tris {(−)-3- (trifluoroacetyl) camphor} europium water. Japanese, tris {(+)-3- (heptafluorobutyryl) camphor} europium hydrate, tris {(−)-3- (heptafluorobutyryl) camphor} europium hydrate, tris {(+) -3- (acetyl) camphor} europium hydrate, tris {(−)-3- (acetyl) camphor} europium hydrate, tris {(+)-3- (pivaloyl) camphor} europium hydrate, tris {(-)-3- (pivaloyl) camphor} europium hydrate and the like can be exemplified.

  This production method is preferably carried out in a solvent in that the yield of the rare earth complex polymer (1) is good. The type of solvent that can be used is not particularly limited as long as the reaction is not inhibited. Examples of usable solvents include alcohols such as methanol, ethanol, propanol and isopropanol, esters such as ethyl acetate, butyl acetate and isoamyl acetate, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether. Glycol ethers, diethyl ether, tert-butyl methyl ether, ethers such as glyme, diglyme, triglyme, tetrahydrofuran, tert-butyl methyl ketone, isobutyl methyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone , Ketones such as cyclohexanone, acetone, hexane, cyclohexane, ethylcyclohexane, heptane, octane, benzene, Toluene, hydrocarbons such as xylene, can be mentioned water. One of these solvents can be used alone, or a plurality of these solvents can be mixed at an arbitrary ratio. As the solvent, methanol or ethanol is preferable because the yield of the rare earth complex polymer (1) is good.

  Next, the molar ratio of the phosphine oxide (5) and the rare earth complex (6) when carrying out this production method will be described. It is preferable to use 0.1 to 10.0 mol, more preferably 0.5 to 1.5 mol of phosphine oxide (5) with respect to 1 mol of the rare earth complex (6).

  In this production method, the reaction temperature and reaction time are not particularly limited, and those skilled in the art can use general conditions for producing a metal complex. As a specific example, the rare earth complex polymer (1) is obtained in a high yield by selecting a reaction time appropriately selected from a range of 1 minute to 120 hours at a reaction temperature appropriately selected from a temperature range of −80 ° C. to 120 ° C. Can be manufactured.

  The rare earth complex polymer (1) produced by this production method can be purified by a person skilled in the art appropriately selecting and using a general purification method for purifying a metal complex. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography and the like.

  The phosphine oxide (5) that can be used in this production method is obtained by the method described in Reference Example 1 of this specification or the method described in Journal of Organic Chemistry, Vol. 32, page 1572 (1967). be able to.

  The rare earth complex (6) that can be used in this production method is obtained by the method described in Reference Example 2 of this specification or the method described in Journal of the American Chemical Society, Vol. 87, page 5254 (1965). It can be obtained.

  Since the rare earth complex polymer of the present invention is excellent in optical properties, it is suitable for optical functional materials. Examples of the optical functional material include a circularly polarizing film and ink.

  By using the rare earth complex polymer (1) of the present invention as a material, an optical functional material having chiral optical properties can be produced.

2 is a result of single crystal X-ray structural analysis of Example 1. FIG. 2 is a result of thermogravimetric analysis by TG in Example 1. FIG. It is a result of the emission spectrum of Example 1. It is a result of the circular dichroism spectrum of Example 1 and Example 2.

Hereinafter, although an example is given and the present invention is explained still in detail, the present invention is not limited to these. Various analyzes were performed under the following conditions. ¹ H-NMR measurement was performed using ECS400 (400 MHz) manufactured by JEOL Ltd., and chemical shift was determined using tetramethylsilane as an internal standard. Elemental analysis was performed using JM10 manufactured by Jay Science Lab or CE-440 manufactured by Exeter Analytical. The ESI-MS measurement used JMS-T100LP manufactured by JEOL Ltd. or Thermo Scientific Exactive manufactured by Thermo Fisher Scientific. For FAB-MS measurement, JMS-700TZ manufactured by JEOL Ltd. was used. R-AXIS manufactured by Rigaku Corporation was used for the single crystal X-ray structural analysis. Thermogravimetric measurement was performed using a Seiko Instruments EXSTAR6000 (TG-DTA6300) in an argon atmosphere at a heating rate of 5 ° C./min. The emission spectrum was measured using a Horiba Fluorolog-3 spectrofluorometer. The circular dichroism spectrum measurement used JASCO J-1100. Methanol, dichloromethane, ethyl acetate, and anhydrous MgSO ₄ were purchased from Kanto Chemical, and tetrahydrofuran was a dehydrated product purchased from Wako Pure Chemical Industries. Europium acetate hydrate is purchased from Wako Pure Chemical Industries, and x representing the number of coordination water in the chemical formula is an arbitrary number.

  Reference example 1

Under a nitrogen gas atmosphere, butyl lithium hexane solution manufactured by Kanto Chemical Co., Ltd. at −78 ° C. was added to a solution obtained by adding 30 mL of dehydrated tetrahydrofuran to 4,4′-dibromobiphenyl (1.91 g, 6.1 mmol) manufactured by Tokyo Chemical Industry. 9.3 mL (1.54 mol / L, 14.3 mmol) was added. After this mixture was stirred at −10 ° C. for 3 hours, 3.2 g (14.5 mmol) of diphenylchlorophosphine manufactured by Tokyo Chemical Industry was added at −78 ° C. After stirring this mixture at room temperature for 14 hours, 70 ml of ethyl acetate and 100 mL of a saturated saline solution were added to carry out a liquid separation operation. Subsequently, the obtained organic layer was washed twice with 100 mL of a saturated saline solution, and the obtained organic layer was dehydrated with anhydrous MgSO ₄ , and then the solvent was dried to obtain a white solid. To a solution obtained by adding 40 mL of dichloromethane to the obtained white solid, 5 mL of 30% H ₂ O ₂ aqueous solution manufactured by Wako Pure Chemical Industries, Ltd. was added at 0 ° C. After stirring this mixture at room temperature for 2 hours, 40 mL of saturated saline solution was added and liquid separation operation was performed. Subsequently, the obtained organic layer was washed twice with 80 mL of saturated saline solution, and the obtained organic layer was dehydrated with anhydrous MgSO ₄ , and then the solvent was evaporated to dryness, 4,4′-bis (diphenylphosphoryl) biphenyl ( dpbp) was obtained as white crystals. (0.780 g, 1.4 mmol, yield 23%) ¹ H-NMR (400 MHz, CDCl ₃ , δ / ppm) 7.65-7.79 (m, 16H, Ar), 7.54-7.59 (M, 4H, Ar), 7.42-7.53 (m, 8H, Ar).
Reference example 2

Europium acetate hydrate (430.9 mg) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 170 mL of pure water and stirred at room temperature for 1.5 hours. A solution of (+)-3- (trifluoroacetyl) camphor [(+)-facam] (802.0 mg, 3.23 mmol) manufactured by Sigma-Aldrich in 20 mL of methanol was added to this solution, and the solution was stirred at room temperature for 17 hours. Stir. The obtained yellow suspension was filtered off to obtain a Eu [(+)-facam] ₃ (H ₂ O) ₂ complex as a yellow solid. (775.5 mg, 0.83 mmol) ESI-MS (m / z) = 917.19 {Eu [(+)-facam] ₃ Na} ⁺ , Anal. Calcd. _{for [C 36 H 46 EuF 9} O 8]: C, 46.51%; H, 4.99%. Found: C, 47.15%; H, 4.87%.
Reference example 3

Europium acetate hydrate (592.4 mg) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 200 mL of pure water and stirred at room temperature for 0.5 hour. To this solution, 12 mL of a methanol solution of (−)-3- (trifluoroacetyl) camphor [(−)-facam] (255.9 mg, 1.03 mmol) manufactured by Sigma-Aldrich was added and stirred at room temperature for 6 hours. The obtained yellow suspension was filtered off to obtain a Eu [(−)-facam] ₃ (H ₂ O) ₂ complex as a yellow solid. (299.4 mg, 0.32 mmol)
Example 1

4,4 ′ prepared in Reference Example 1 was added to a solution obtained by adding 3 mL of methanol to Eu [(+)-facam] ₃ (H ₂ O) ₂ complex (185.9 mg, 0.20 mmol) prepared in Reference Example 2. A solution of 7.7 mL of methanol in bis (diphenylphosphoryl) biphenyl (dpbp) (110.9 mg, 0.20 mmol) was added. The mixture was stirred at 70 ° C. for 24 hours. By filtering off the obtained white suspension, tris {(+)-3- (trifluoroacetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer [Eu (dpbp) [ (+)-Facam] ₃ ] ₁ was obtained as a white solid. (154.2 mg, 0.106 mmol, 53%) FAB-MS (m / z) = 1201.2 [Eu (dpbp) [(+)-facam] ₂ (dpbp)] ⁺ , Anal. Calcd. _{for [C 72 H 70 EuF 9} O 8 P 2]: C, 59.71%; H, 4.87%. Found: C, 59.47%; H, 4.86%.
The crystals used for the single crystal X-ray structure analysis were synthesized by the following method. The Eu [(+)-facam prepared in Reference Example 2 was added to 0.5 mL of a dichloromethane solution of 4,4′-bis (diphenylphosphoryl) biphenyl (dpbp) (16.5 mg, 0.03 mmol) prepared in Reference Example 1. ] 0.5 mL of a methanol solution of ₃ (H ₂ O) ₂ complex (18.3 mg, 0.02 mmol) was added so that an interface was formed, and after standing at room temperature for 8 days, [Eu (dpbp) [ (+)-Facam] ₃ ] _l crystals were obtained.

The obtained [Eu (dpbp) [(+)-facam] ₃ ] _l was analyzed by single crystal X-ray structural analysis. The obtained results are shown in FIG. For one Eu (III) ion, two molecules of dpbp are coordinated at two positions, and three molecules of [(+)-facam] are coordinated at six positions. It was found that was formed.

[Eu (dpbp) [(+)-facam] ₃ ] _{1 was} subjected to thermogravimetric analysis by TG. The obtained results are shown in FIG. It was found that the thermal decomposition temperature of [Eu (dpbp) [(+)-facam] ₃ ] _l was 356 ° C.

FIG. 3 shows a solid state emission spectrum of [Eu (dpbp) [(+)-facam] ₃ ] _l excited by 380 nm (ligand excitation). Emissions of 593 nm, 612 nm, 655 nm, and 699 nm based on Eu (III) ff electronic transition were observed.

The circular dichroism spectrum of [Eu (dpbp) [(+)-facam] ₃ ] _l is shown in FIG. For the measurement, tetrahydrofuran for spectroscopic analysis manufactured by Wako Pure Chemical Industries, Ltd. was used, and a solution having a concentration of 2.0 × 10 ⁻⁵ M was used for the measurement. As a result, chiral photophysical properties were observed.

  Example 2

4 prepared in Reference Example 1 was added to a solution obtained by adding 3.2 mL of methanol to Eu [(−)-facam] ₃ (H ₂ O) ₂ complex (184.6 mg, 0.20 mmol) prepared in Reference Example 3. A solution of 8.7 mL of methanol in 4′-bis (diphenylphosphoryl) biphenyl (dpbp) (110.2 mg, 0.20 mmol) was added. The mixture was stirred at 70 ° C. for 14 hours. By filtering off the obtained white suspension, tris {(−)-3- (trifluoroacetyl) camphor} {4,4′-bis (diphenylphosphoryl) biphenyl} europium polymer [Eu (dpbp) [ (−)-Facam] ₃ ] ₁ was obtained as a white solid. (183.0 mg, 0.13 mmol, 64%)
The circular dichroism spectrum of [Eu (dpbp) [(−)-facam] ₃ ] _l is shown in FIG. For the measurement, tetrahydrofuran for spectroscopic analysis manufactured by Wako Pure Chemical Industries, Ltd. was used, and a solution having a concentration of 2.0 × 10 ⁻⁵ M was used for the measurement. As a result, chiral photophysical properties were observed.

Claims (10)

General formula (1)

(In the formula, A represents a divalent organic group, L represents an acetylacetone group, and at least one of A and L is optically active. R ¹ , R ² , R ³ and R ⁴ are each independently Represents an alkyl group having 1 to 10 carbon atoms, or a monovalent aromatic group which may have a substituent, n represents an integer of 1 to 20, and m represents an integer of 1 to 4. Represents an integer of 1 to 100000. Ln represents a trivalent rare earth ion.) L is the general formula (2)

(In the formula, R ⁵ represents either an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms. X ¹ and X ² are bonded to each other to form a ring structure. The rare earth complex polymer according to claim 1, which is an optically active acetylacetone ligand represented by formula (1): L is the general formula (2a)

(In the formula, R ⁵ has the same meaning as R ^{5 in} formula (2). R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen, deuterium atom, or halogen atom. 3 represents an alkyl group having 1 to 6 carbon atoms and a methylene sulfonic acid derivative group.) The rare earth complex polymer according to claim 1 or 2. A is the general formula (3)

(In the formula, n represents the same meaning as n in formula (1). R ¹² represents a halogen atom or an alkyl group having 1 to 6 carbon atoms, and k represents a substitution in a ring to which R ¹² is bonded to 0 to R ^12. An integer up to the number of possible sites, and when k is 2 or more, the plurality of R ¹² may be the same or different from each other. 3. The rare earth complex polymer according to 3. The complex polymer according to claim 1, wherein the rare earth ion is Eu (trivalent). Chemical formula (4)

The complex polymer according to any one of claims 1 to 5, which is represented by the formula: (wherein any one of R ⁶ and R ⁷ is a methyl group and the other is a hydrogen atom). General formula (5)

Represented ^(wherein, R ^{1, R 2, R 3, R 4} , A and n are ^R 1 in the general formula (1) ^{represents R 2, R 3, R 4} , A and n synonymous.) In Phosphine oxide;
General formula (6)

(Wherein Y represents a coordination molecule. J represents an integer of 0 to 6. L, Ln and m have the same meaning as L, Ln and m in formula (1)). The method for producing a rare earth complex polymer according to any one of claims 1 to 6, wherein: An optical functional material comprising the rare earth complex polymer according to claim 1. A circularly polarizing filter comprising the rare earth complex polymer according to claim 1. An ink comprising the rare earth complex polymer according to claim 1.

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